Gasoline containing n-sulfinyl amine

ABSTRACT

GASOLINE CONTAINING AS AN ANTIKNOCK AGENT AN N-SULFINYL AMINE COMPOUND, IS DESCRIBED.

United States Patent Ofice GASOLINE CONTAINING N-SULFINYL AMINE GeorgeC. Licke, Oxford, Mich., assignor to Ethyl Corporation, New York, N.Y.,a corporation of Virginia N Drawing. Filed Dec. 20, 1968, Ser. No.785,804 Int. Cl. C101 1/22 U.S. Cl. 44-74 10 Claims ABSTRACT OF THEDISCLOSURE Gasoline, containing as an antiknock agent an N-sulfinylamine compound, is described.

BACKGROUND OF THE INVENTION This invention is directed to the use ofN-sulfinyl amines as gasoline antiknock agents.

The octane number of a gasoline is improved by addition of an antiknockagent. The most commonly used antiknock agents are organolead compoundssuch as tetraethyllead. Sulfur containing compounds in gasoline, on theother hand, are generally detrimental to octane number.

The present invention provides a novel, sulfur containing non-metallicorganic compound as an antiknock agent.

SUMMARY OF THE INVENTION Gasoline containing an antiknock quantity of anN- sulfinyl amine.

DESCRIPTION OF PREFERRED EMBODIMENTS An embodiment of this invention isgasoline containing an antiknock quantity of a compound having theformula R- [N SOH- (I) wherein x is an integer from 1 to 4 inclusive,preferably 1 to 2 inclusive, and R is selected from (a) C -C alkylgroups (b) C C aryl groups (c) C -C alkenyl groups, and

(d) alkylene amino groups having the formula where R and R areindependently selected from hydrocarbon alkyl groups having from 2 toabout 4 carbon atoms, and y is 0 to 6. Gasoline which is substantiallyfree of organolead compounds is preferred.

Another preferred gasoline composition contains N- sulfinyl aryl amineshaving 6 to about 30 carbon atoms. The amount of N-sulfinyl aminecompound present in the gasoline ranges from 0.1 to about 10 gram-molsper gallon. The N-sulfinyl mononuclear aryl amines having 6 to 18 carbonatoms are more preferred. N-sulfinyl aniline and N-sulfinyl substitutedanilines such'as N-sulfinyl toluidine are especially preferred.

The N-sulfinyl amines used in the invention are defined by Formula Iabove. Methods of preparing these compounds are available in the art. Arepresentative method of preparing these compounds is direct treatmentof the parent primary amine with thionyl chloride in a suitable3,554,712 Patented Jan. 12, 1971 solvent. The reaction is illustrated bythe following equation:

As the equation illustrates, an N-sulfinyl amine is a derivative of aprimary amine in which the two amine hydrogens are replaced by theradical. In general then, the N-sulfinyl derivative of any suitableprimary amine can be used as a gasoline anti-knock in the practice ofthis invention, provided that it has sufiicient solubility in gasolineto effect octane number improvement.

Preferred N-sulfinyl amines are those in which the R in the Formula Iabove is selected from the Groups (a)- (d) listed above. N-sulfinylamines in which R is a C -C alkyl group include linear, cyclic, andbranched alkyl groups with one or more sulfinyl moieties. Representativeexamples of N-sulfinyl amines are:

N-sulfinyl-n-pentylamine, N-sulfinyl-n-octadecylamine,N-sulfinyl-2-ethyl-n-hexylamine,N-sulfinyl-2,4,4,6,G-pentamethyl-n-heptylamine, N-sulfinylcyclohexylamine,

N-sulfinyl cyclopentylamine,

N-sulfinyl cyclooctylamine,

N-sulfinyl laurylamine,

and the like.

Representative examples of N-sulfinyl alkyl amines having more than onesulfinyl group are:

N,N-disulfinyl-1,5-pentanediamine,

N,N-disulfinyl-l,lO-decanediamine,

N,N',N",N-tetrasulfinyl-(2,3 methylamine) 1,4 butanediamine,

N,N',N"-trisulfinyl-l,6,l2-dodecanetriamine N,N-disulfinyll l8-octadecanediamine,

and the like.

N-sulfinyl amines wherein R in Formula I is a C -C aryl group can haveone or more sulfinyl groups; and R can be an unsubstituted aryl group,substituted aryl group, alkaryl and aralkyl group, mononuclear as wellas polynuclear aryl group. Representative examples of these N-sulfinylaryl amines are:

N-sulfinyl-p-cyclohexylaniline, N-sulfinyl-2,-dichloroaniline,N-sulfinyl-[i-naphthylamine, N-sulfinyl-4-diphenylamine,N-sulfinyl-4-dodecylaniline, N-sulfinyl-2,4-didodecylaniline,N-sulfinyl-2,4'dimethylamine,

N-sulfinyl benzylamine, N-sulfinyl-a-anthracenylamine,N-sulfinyl-Z-isopropylaniline, N-sulfinyl-4-octadecylaniline,N-sulfinyl-2,4,6-triethylaniline, N-sulfinyl-N'-phenyl-phenylenediamine,N,N'-disulfinyl-4,4'-diphenyldiamine,N,N,N"-trisulfinyl-l,3,5-benzenetriamine,N,N',N",N"'-tetrasulfinyl-1,2,4,6-benzene tetramine,N,N'-disulfinyl-benzidine, N,N'-disulfinyl-3,3'-dichlorobenzidine, andthe like.

More preferred N-siilfinyl aryl amines are those derived from lower arylmononuclear mono and diamines having from 6 to about 18 carbon atoms.Representative examples of these N-sulfinyl aryl amines are:

N-sulfinyl amines where R in Formula I is an alkenyl group includemonoas well as poly-unsaturated alkenyl compounds. Representativeexamples of these N-sulfinyl alkenyl amines are N-sulfinyl allylamine.N-sulfinyl oleylamine, N-sulfinyl linoleylainine, N-sulfinyl-4-pentenvlamine, N-sulfinyl-Z-heptenyl amine, N.N'-disulfinyl-6-dodecenyl-l,l2-diamine, and the like.

N-sulfinyl amines where R is the group represented by [RFLU R wherein RR and y are as defined above. are derived from C C alkylene diamines andpolyamines. Representative examples of these types of N-sulfinyl aminesare:

Mixtures of N-sulfinyl amine compounds described above can also be usedin gasoline compositions of the present invention.

Any gasoline suitable for use in internal combustion engines may be usedin the practice of this invention. By

gasoline is meant a hydrocarbon or blend of hydrocarbons boiling in therange from about 25 C. to about 250 C. which occur naturally inpetroleum as Well as suitable hydrocarbons manufactured from petroleum.for example. by thermal or catalytic cracking, polymerizing, reforming,and the like. Typical gasolines are listed in Table I.

TABLE I.IIYD ROCARBON COMPOSITION OF BASE GASOLINES Base gasoline lI\'(llOCt1ll)0l1 type A '3 C D E T Aromatics. percent L10. 27. 0 34. 519.0 .0 Oltlnis. percent" 4.5 11. 0 K. 0 1R. 5 .5 Siittirntt-s. pun-t ts5. 0 62. i) 07 5 l3). 5 '3 J, in the handling of gasolines inrefineries, tanks. pipelines, tc the gasoline may pick up traces oforganolead com- 10unt1s. The term "substantially free of organoleadcomounds indicates gasoline that has picked up this minor generally lessthan about 0.1 gram of lead per gallon) .mount of organolead compounds.

"he amount of N-sulfinyl amine which is added to the me gasoline toprepare gasoline compositions of the resent invention may be aried. Theterm "antiknock auantity means an amount of N-sulfinyl amine sutficient0 increase the octane number or' the base gasoline. Gen- :raily fromabout 0.1 to about 10 gram-mols of the l uifinyl amine can be added pergallon of base gasoline. l gram-mol is the molecular weight of the amineexpressed in grams. For example. if the N-sulfinyl amine .dditive has amolecular weight of 100 then gasoline comiositions or the presentinvention could contain as little is l gram or as much as 1000 grams ofthe amine per gallon of gasoline.

The gasoline compositions of the present invention do tot require anyspecial method of preparation. The addiive can simply be added directlyto the gasoline and .tlended using any conventional blending means. Inaddition to the novel N-sulfinyl amine antiknock additive. the presentgasoline composition may contain other additives arovided that they donot adversely affect the function it the N-sulfinyl amine; such gasolineadditives include ion-organolead antiknock agents such as (cyclopentadi-:nyllmanganese tricarbonyl. antioxidants such as the hindered phenols.dyes. anti-icing additives. carburetor detergents such as fatty acidamino-amides. corrosion innibitors. metal deactivators. and the like. Ifdesired, antitnock fluids or concentrates may be prepared containing heN-sulfinyl amines and any combination of other additives and/ordiluents.

he feature of the present invention is that the N-sullnyl aminesdescribed above are antiknock agents in gasliines. In other words.gasolines containing N-sulfinyl tmines have improved octane ratings,This was demonstrated by blending a series of fuels containing fromabout 0.5% to about 5.0% by volume of certain N-sulfinyl mines. TheResearch Octane Number (RON) of the base uel alone and the base fuelcontaining the sulfinyl addiwe were determined using the method of ASTMD908. The antiknock effect was expressed as the difference ARON) betweenthese two Research Octane Numbers. "he data obtained for a series offuel compositions demtnstrating this antiknock erfect is contained inTable II "elow.

ABLE II. NSULFINYLAMINES IN BASE GASOLINE A.

.mount of idditive 'olume. percent .xainple additive urinals/gal.) RON lARON '17. 65 E8. 05 l. 40 )8. l. 55 )8. 00 1.

. 97.90 0. 5 )8. 15 I. 25 ido l. 0 )8. 0. .lo 5.0 100.40 3.50 t.q-Slllfillyltlllllllm 5. 0 100. 35 J. l5

kvcrage of two determinations.

The Research Octane Number data of Examples l9 amply illustrate thebeneficial effect of N-sulfinyl amines n gasoline.

The following examples further illustrate compositions 0 of the presentinvention. These compositions are prepared TABLE III Base gasolineExample Additive Amount of N-sulfinyl-p-tert-butylaniline. N,N-disulfinyl-1,3-propane diamlne N -sultlnyl-4-pentenylamiueN-sulflnylcyelohexylamiue The gasoline compositions of the presentinvention have been fully described above. Data is presented to show theantiknock efiectiveness of the N-sulfinyl amines in these gasolinecompositions.

I claim:

1. Gasoline containing an antiknock quantity of a compound having theformula R- [N=SO] wherein x is an integer from 1 to 4 inclusive and R isselected from the group consisting of (a) C C alkyl groups (b) C -C arylgroups (c) C -C alkenyl groups, and

(d) alkylene amino groups having the formula 4. A gasoline of claim 2wherein R is a C -C aryl group.

5. A gasoline of claim 3 wherein x is an integer from 1 to 2 inclusive.

6. A gasoline of claim 4 wherein R is a C -C mononuclear aryl group.

7. The gasoline of claim 6 wherein said compound isN-sulfinyl-p-toluidine.

8. A gasoline of claim 6 wherein said compound is N-sulfinyl aniline.

9. A gasoline of claim 7 wherein the concentration of said compound isfrom about 0.5 to about 5% by volume.

10. A gasoline of claim 8 wherein the concentration of said compound isfrom about 0.5 to about 5% by volume.

U.S. C1. X.R.

